EP0448946B1 - Electrically conductive stannic oxide - Google Patents

Electrically conductive stannic oxide Download PDF

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Publication number
EP0448946B1
EP0448946B1 EP91102065A EP91102065A EP0448946B1 EP 0448946 B1 EP0448946 B1 EP 0448946B1 EP 91102065 A EP91102065 A EP 91102065A EP 91102065 A EP91102065 A EP 91102065A EP 0448946 B1 EP0448946 B1 EP 0448946B1
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Prior art keywords
tin
oxide
mixture
fluoride
temperatures
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German (de)
French (fr)
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EP0448946A3 (en
EP0448946A2 (en
Inventor
Erich Dr. Ruf
Joachim Giersberg
Hartmut Gomm
Gerd Dembinski
Hans-Günter Krohm
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Evonik Operations GmbH
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TH Goldschmidt AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/675—Oxides, hydroxides or carbonates
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0902—Inorganic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09708—Inorganic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

  • the invention relates to a method for producing an electrically conductive tin IV oxide with at most 2% divalent tin and 0.1 to 2.5% halides.
  • Such preparations are often applied by spray atomization to previously heated substrates, in particular to previously heated glass.
  • electrically conductive, infrared-reflecting, but substrate-bound tin oxide layers are produced by pyrolytic or pyrogenic decomposition of the compounds present in such preparations.
  • the electrical conductivity is generated by defects in the respective tin oxide layers, such defects being largely formed by the added dopants.
  • defects in the respective tin oxide layers such defects being largely formed by the added dopants.
  • Donor terms are generated from which, if necessary, electrons can be brought into the conduction band with little expenditure of energy. This is not the case with pure, undoped tin oxide due to the forbidden zone between the valence band and the conduction band.
  • electrical conductivity or an antistatic setting of various solid and liquid technical products such as.
  • plastics, paints and inks, papers, toners and textiles electrically conductive pigments are required.
  • powdered semiconductors are often used. It is desirable to have white or to be able to use light-colored, fine-grained semiconductor pigments with high electrical conductivity or low specific resistance.
  • Antimony-doped conductive tin oxides are already as such and on carrier materials, such as. B. applied titanium oxide, known.
  • carrier materials such as. B. applied titanium oxide
  • electrically conductive tin oxides have disadvantages. Due to the antimony doping, such conductive tin oxides are colored blue to different extents depending on the antimony content and the annealing temperature.
  • tin oxides containing antimony oxide and substances containing antimony oxide in general do not appear to be safe from an occupational medical perspective.
  • GB-A-1 517 341 describes a solution which contains a thermally decomposable tin salt, which can be doped with antimony fluoride or hydrofluoric acid, among other things.
  • Transparent tin oxide films are obtained on the glass surface. Ethers, esters or alcohols are used as solvents.
  • GB-A-2 080 275 also describes a conductive element on which there is a layer of polycrystalline tin oxide which is doped with tin fluoride.
  • the invention is based on the object of providing halide-doped tin IV oxides which are as light as possible and which can be prepared as simply as possible and from readily accessible raw materials.
  • the process according to the invention is characterized in that tin-II-oxide or tin-IV-oxide is mixed with, based on the mixture, up to 20% by weight of tin-II-fluoride or an equivalent amount of hydrofluoric acid, the mixture in one Temperature range from 200 to 700 ° C glows and the glow product is ground until the desired particle size is reached.
  • Low molecular weight alcohols are preferably added to the mixture of tin (II) oxide and tin (II) fluoride or hydrofluoric acid.
  • methanol or ethanol is used as the alcohol.
  • solid tin (II) oxide instead of the solid tin (II) oxide, freshly precipitated tin (II) hydroxides or basic tin (II) hydroxide products can also be reacted with solid tin (II) fluoride.
  • tin (II) oxide and tin (IV) oxide can also be used in the process according to the invention.
  • Another method according to the invention consists in first precipitating basic tin-II compounds and / or basic tin-II hydroxides from tin-II salt solutions in a manner known per se, washing the precipitated products obtained several times, then washing them with 5 to 70 % By weight, based on precipitated basic tin-II compounds, stirres II-fluoride in the form of an aqueous solution for a period of 5 to 60 minutes, which separates the doped precipitation products from the solution, washed out, at temperatures of 100 to Dries 200 ° C, then glows at temperatures of 200 to 700 ° C and grinds the glow product until the desired particle size is reached.
  • Another process according to the invention is characterized in that 10 to 100% by weight, based on tin-II-halide, of alkylene oxide is introduced into aqueous tin-II-halide solutions, the precipitated products obtained are separated from the solution, washed out at temperatures of 100 dries to 200 ° C, then glows at temperatures from 200 to 700 ° C and grinds the glow product until the desired particle size is reached.
  • ethylene oxide is used as the alkylene oxide. If ethylene oxide is introduced into a tin (II) chloride solution which contains sufficient amounts of tin (II) fluoride in solution for doping, tin (II) hydroxide chloride, optionally with a little tin (II) hydroxide, precipitates practically quantitatively.
  • iodine-doped electrically conductive tin oxides are also produced in a simple manner by mixing mixtures of tin-II-oxide and tin-IV-oxide with, based on the mixture, up to 20% by weight of tin-II-halide, the mixture glows in a temperature range of 200 to 700 ° C and grinds the glow product until the desired particle size is reached.
  • the halide-doped electrically conductive tin oxides produced according to the invention are gray to light-colored depending on the production, type and amount of the doping.
  • those doped with fluoride are somewhat superior to those doped with chloride, bromide and iodide in terms of their electrical conductivity and temperature resistance.
  • the chloride and / or bromide or. Iodine doping is superior to fluoride doping in terms of color in that they are lighter in color.
  • the conductive tin IV oxides produced according to the invention have a specific resistance of ⁇ 50 ⁇ . m, the measured values for fluorine-doped tin IV oxide mostly ⁇ 10 ⁇ . m, in particular about 0.3 to 2 ⁇ . m.
  • the compounds produced according to the invention can be used in particular as fillers or pigments in plastics, paints, paints, paper, textiles and toners.
  • the processes according to the invention have in common that the products obtained are annealed in different ways. As already stated, this annealing takes place at approximately 200 to 600 ° C. A range of approximately 300 to 500 ° C. is preferred.
  • the electrically conductive tin oxide thus obtained has a specific resistance of 1.3 ⁇ . m on.
  • the tin II content is ⁇ 0.3%.
  • the fluoride content is 0.9%.
  • stannous oxide In a mortar mill, 250 g of stannous oxide, 14.75 g of stannous chloride and 14.75 g of stannous fluoride are intimately mixed by grinding for 10 minutes. The mixture of substances thus obtained is annealed in a corundum dish at 300 ° C. for 1 hour. After cooling, the electrically conductive tin oxide obtained in this way is ground again in a mortar mill for 10 minutes.
  • the electrically conductive tin oxide obtained has a specific resistance of 1 ⁇ . m on.
  • the tin II content is 0.8%.
  • the fluoride content is included 0.49%.
  • the chloride content is included 0.3%.
  • tin IV oxide 125 g
  • 14.75 g of tin II fluoride are intimately mixed by grinding for 10 minutes.
  • the mixture of substances thus obtained is then placed in a corundum bowl Annealed for 1 hour at 300 ° C. After cooling, the annealed product is ground again in a mortar mill for 10 minutes.
  • the electrically conductive tin oxide thus obtained has a specific resistance of 12 ⁇ . m on.
  • the tin II content is ⁇ 0.3%.
  • the fluoride content is 0.9%.
  • stannous oxide 250 g are stirred in a beaker with a 70% methanolic stannous chloride solution for 20 minutes. The supernatant aqueous phase is then decanted off. The product thus obtained is dried at 200 ° C. for 1 hour and then annealed in a corundum dish at 500 ° C. for 1 hour. During the glow period, the product is mixed by crying once. After cooling, the glow product is ground in a mortar mill.
  • the electrically conductive tin oxide thus obtained has a specific resistance of 8 ⁇ . m on.
  • the tin II content is 0.5%.
  • the chloride content is ⁇ 0.3%.
  • stannous oxide and 29.5 g of stannous iodide are intimately mixed by grinding for 10 minutes.
  • the mixture of substances thus obtained is annealed in a corundum dish at 500 ° C. for 1 hour.
  • the product is mixed by crying once.
  • the glow product is then ground again in a mortar mill for 10 minutes.
  • An electrically conductive tin oxide is obtained which has a specific resistance of 36 ⁇ . m has.
  • the tin II content is 1.8%.
  • the iodide content is 1.2%.
  • stannous oxide and 34.0 g of hydrobromic acid (48% strength) are intimately mixed with one another by grinding for 10 minutes.
  • the mixture of substances thus obtained is annealed in a corundum dish at 500 ° C. for 1 hour. During the glow period, the product is mixed by crying once. After cooling, the annealed product is ground again in a mortar mill for 10 minutes.
  • the electrically conductive tin oxide thus obtained has a specific resistance of 40 ⁇ . m on.
  • the tin II content is ⁇ 0.3%.
  • the bromide content is 1.0%.
  • the product obtained in this way is then annealed in a corundum dish at 500 ° C. for 1 hour. During the glow period, the product is mixed by crying once. After cooling, the annealed product is ground in a mortar mill for 10 minutes.
  • the tin II content is ⁇ 0.3%.
  • the chloride content is 0.5%.
  • the fluoride content is 1.2%.
  • the tin II content is ⁇ 0.3%.
  • the chloride content is 0.4%.
  • a white precipitate is obtained which is washed five times with 2.5 l of water each time.
  • the precipitated product washed in this way is then dried in a porcelain dish at 110 ° C. (12 hours) and then annealed in a corundum crucible at 500 ° C. for 1 hour. While the glowing time, the product is mixed once crowing. After annealing and cooling, the product is sieved through a 630 ⁇ m sieve and the sieve pass is annealed again at 500 ° C. for 15 minutes.
  • the glow product thus obtained is sieved through a 100 ⁇ m sieve.
  • the electrically conductive tin oxide thus obtained as a sieve has a specific resistance of 0.3 ⁇ . m.
  • the tin II content is ⁇ 0.3%.
  • the fluoride content is 1 %.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Conductive Materials (AREA)

Description

Die Erfindung betrifft ein Verfahren zur Herstellung eines elektrisch leitfähigen Zinn-IV-oxids mit höchstens 2 % zweiwertigem Zinn und 0,1 bis 2,5 % Halogeniden.The invention relates to a method for producing an electrically conductive tin IV oxide with at most 2% divalent tin and 0.1 to 2.5% halides.

Es ist seit langem bekannt, elektrisch leitfähige und infrarotreflektierende Zinnoxidschichten auf Substrate, insbesondere auf Glas, aufzubringen. Vielfach erfolgt die Herstellung solcher auf Substrate bzw. auf Glas aufgebrachten elektrisch leitfähigen und infrarotreflektierenden Zinnoxidschichten durch pyrolytische Zersetzung von flüssigen Zubereitungen, die im wesentlichen eine oder mehrere Basis-Zinnverbindungen und eine oder mehrere geeignete fluoridhaltige Dotierungsverbindungen enthalten.It has long been known to apply electrically conductive and infrared-reflecting tin oxide layers to substrates, in particular to glass. Such electrically conductive and infrared-reflecting tin oxide layers applied to substrates or to glass are often produced by pyrolytic decomposition of liquid preparations which essentially contain one or more base tin compounds and one or more suitable fluoride-containing doping compounds.

Über solche substratgebundene, elektrisch leitfähige und infrarotreflektierende Zinnoxidschichten bzw. über die hierfür zum Einsatz kommenden flüssigen Zubereitungen gibt es eine Vielzahl Veröffentlichungen und Patente.There are numerous publications and patents on such substrate-bound, electrically conductive and infrared-reflecting tin oxide layers or on the liquid preparations used for this purpose.

Solche Zubereitungen werden vielfach im Sprühzerstäubungsverfahren auf zuvor erhitzte Substrate, insbesondere auf zuvor erhitztes Glas, aufgebracht. Hierdurch werden durch pyrolytische bzw. pyrogene Zersetzung der in solchen Zubereitungen vorhandenen Verbindungen elektrisch leitfähige, infrarotreflektierende, jedoch substratgebundene Zinnoxidschichten erzeugt.Such preparations are often applied by spray atomization to previously heated substrates, in particular to previously heated glass. In this way, electrically conductive, infrared-reflecting, but substrate-bound tin oxide layers are produced by pyrolytic or pyrogenic decomposition of the compounds present in such preparations.

Die elektrische Leitfähigkeit wird durch Fehlstellen in den jeweiligen Zinnoxidschichten, wobei solche Fehlstellen zum größten Teil durch die zugesetzten Dotierungsmittel gebildet werden, erzeugt. Hierbei werden nur wenig unterhalb des Leitungsbandes Störstellenterme resp. Donatorterme erzeugt, aus denen gegebenenfalls unter geringem Energieaufwand Elektronen in das Leitungsband gebracht werden können. Dies ist bei reinem, undotiertem Zinnoxid aufgrund der zwischen Valenzband und Leitungsband vorhandenen verbotenen Zone nicht der Fall.The electrical conductivity is generated by defects in the respective tin oxide layers, such defects being largely formed by the added dopants. Here are just a little below the conduction band impurity terms. Donor terms are generated from which, if necessary, electrons can be brought into the conduction band with little expenditure of energy. This is not the case with pure, undoped tin oxide due to the forbidden zone between the valence band and the conduction band.

Im Hinblick auf elektrische Leitfähigkeit bzw. einer antistatischen Einstellung von verschiedenen festen und flüssigen technischen Produkten, wie z. B. Kunststoffe, Lacke und Farben, Papiere, Toner und Textilien, werden elektrisch leitfähige Pigmente benötigt. Neben Metallpulvern und Graphit, die zwangsläufig eine dunkle Einfärbung solcher technischen Produkte nach sich ziehen, werden vielfach pulverförmige Halbleiter zum Einsatz gebracht. Hierbei ist es wünschenswert, möglichst weiße resp. hellfarbene, feinkörnige Halbleiterpigmente mit hoher elektrischer Leitfähigkeit bzw. geringem spezifischen Widerstand einsetzen zu können.With regard to electrical conductivity or an antistatic setting of various solid and liquid technical products, such as. As plastics, paints and inks, papers, toners and textiles, electrically conductive pigments are required. In addition to metal powders and graphite, which inevitably result in the dark coloring of such technical products, powdered semiconductors are often used. It is desirable to have white or to be able to use light-colored, fine-grained semiconductor pigments with high electrical conductivity or low specific resistance.

Antimondotierte leitfähige Zinnoxide sind bereits als solche und auf Trägermaterialien, wie z. B. Titanoxid aufgebracht, bekannt. Solche elektrisch leitfähigen Zinnoxide weisen jedoch Nachteile auf. Aufgrund der Antimondotierung sind solche leitfähigen Zinnoxide je nach Antimongehalt und Glühtemperatur unterschiedlich stark blau eingefärbt. Ferner kommt hinzu, daß antimonoxidhaltige Zinnoxide sowie allgemein antimonoxidhaltige Stoffe heute arbeitsmedizinisch nicht unbedenklich erscheinen.Antimony-doped conductive tin oxides are already as such and on carrier materials, such as. B. applied titanium oxide, known. However, such electrically conductive tin oxides have disadvantages. Due to the antimony doping, such conductive tin oxides are colored blue to different extents depending on the antimony content and the annealing temperature. In addition, tin oxides containing antimony oxide and substances containing antimony oxide in general do not appear to be safe from an occupational medical perspective.

In der GB-A-1 517 341 wird eine Lösung beschrieben, die ein thermisch zersetzbares Zinnsalz enthält, welches u.a. mit Antimonfluorid oder Flußsäure dotiert sein kann. Es werden dabei transparente Zinnoxidfilme auf der Glasoberfläche erhalten. Als Lösungsmittel werden Ether, Ester oder Alkohole verwendet.GB-A-1 517 341 describes a solution which contains a thermally decomposable tin salt, which can be doped with antimony fluoride or hydrofluoric acid, among other things. Transparent tin oxide films are obtained on the glass surface. Ethers, esters or alcohols are used as solvents.

Weiter wird in der GB-A-2 080 275 ein leitfähiges Element beschrieben, auf dem sich eine Schicht aus polykristallinem Zinnoxid befindet, welches mit Zinnfluorid dotiert ist.GB-A-2 080 275 also describes a conductive element on which there is a layer of polycrystalline tin oxide which is doped with tin fluoride.

Der Erfindung liegt die Aufgabe zugrunde, halogeniddotierte, möglichst hellfarbene Zinn-IV-oxide bereitzustellen, die möglichst einfach und aus gut zugänglichen Rohstoffen herstellbar sind.The invention is based on the object of providing halide-doped tin IV oxides which are as light as possible and which can be prepared as simply as possible and from readily accessible raw materials.

Das erfindungsgemäße Verfahren ist dadurch gekennzeichnet, daß man Zinn-II-oxid oder Zinn-IV-oxid mit, bezogen auf Gemisch, bis zu 20 Gew.-% Zinn-II-fluorid oder einer äquivalenten Menge Flußsäure mahlend vermischt, das Gemisch in einem Temperaturbereich von 200 bis 700° C glüht und das Glühprodukt bis zum Erreichen der gewünschten Teilchengröße mahlt.The process according to the invention is characterized in that tin-II-oxide or tin-IV-oxide is mixed with, based on the mixture, up to 20% by weight of tin-II-fluoride or an equivalent amount of hydrofluoric acid, the mixture in one Temperature range from 200 to 700 ° C glows and the glow product is ground until the desired particle size is reached.

Vorzugsweise setzt man dem Gemisch aus Zinn-II-oxid und Zinn-II-fluorid bzw. Flußsäure niedermolekulare Alkohole zu. Als Alkohole verwendet man insbesondere Methanol oder Ethanol.Low molecular weight alcohols are preferably added to the mixture of tin (II) oxide and tin (II) fluoride or hydrofluoric acid. In particular, methanol or ethanol is used as the alcohol.

Anstelle des festen Zinn-II-oxids kann man auch frisch gefällte Zinn-II-hydroxide oder basische Zinn-II-hydroxidprodukte mit festem Zinn-II-fluorid umsetzen.Instead of the solid tin (II) oxide, freshly precipitated tin (II) hydroxides or basic tin (II) hydroxide products can also be reacted with solid tin (II) fluoride.

Man kann auch Gemische von Zinn-II-oxid und Zinn-IV-oxid bei dem erfindungsgemäßen Verfahren einsetzen.Mixtures of tin (II) oxide and tin (IV) oxide can also be used in the process according to the invention.

Ein anderes erfindungsgemäßes Verfahren besteht darin, daß man zunächst in an sich bekannter Weise aus Zinn-II-salzlösungen basische Zinn-II-verbindungen und/oder basische Zinn-II-hydroxide ausfällt, die erhaltenen Fällungsprodukte mehrmals auswäscht, sodann diese mit 5 bis 70 Gew.-%, bezogen auf ausgefällte basische Zinn-II-verbindungen, Zinn-II-fluorid in Form einer wäßrigen Lösung während eines Zeitraumes von 5 bis 60 Minuten rührt, die dotierten Fällungsprodukte von der Lösung abtrennt, auswäscht, bei Temperaturen von 100 bis 200° C trocknet, dann bei Temperaturen von 200 bis 700° C glüht und das Glühprodukt bis zum Erreichen der gewünschten Teilchengröße mahlt.Another method according to the invention consists in first precipitating basic tin-II compounds and / or basic tin-II hydroxides from tin-II salt solutions in a manner known per se, washing the precipitated products obtained several times, then washing them with 5 to 70 % By weight, based on precipitated basic tin-II compounds, stirres II-fluoride in the form of an aqueous solution for a period of 5 to 60 minutes, which separates the doped precipitation products from the solution, washed out, at temperatures of 100 to Dries 200 ° C, then glows at temperatures of 200 to 700 ° C and grinds the glow product until the desired particle size is reached.

Es ist auch möglich, daß man in an sich bekannter Weise aus Zinn-II-salzlösungen basische Zinn-II-verbindungen und/oder basische Zinn-II-hydroxide ausfällt, die Fällung in Gegenwart von 1 bis 70 Gew.-%, bezogen auf ausgefällte basische Zinn-II-verbindungen, Zinn-II-fluorid durchführt und die dotierten Fällungsprodukte von der Lösung abtrennt, auswäscht, bei Temperaturen von 100 bis 200° C trocknet, dann bei Temperaturen von 200 bis 700° C glüht und das Glühprodukt bis zum Erreichen der gewünschten Teilchengröße mahlt.It is also possible to precipitate basic tin-II compounds and / or basic tin-II hydroxides from tin-II salt solutions in a manner known per se, the precipitation in the presence of 1 to 70% by weight, based on Precipitated basic tin-II compounds, tin-II-fluoride and the doped precipitation products separated from the solution, washed, dried at temperatures from 100 to 200 ° C, then annealed at temperatures from 200 to 700 ° C and the annealing product until Reaching the desired particle size grinds.

Ein weiteres erfindungsgemäßes Verfahren ist dadurch gekennzeichnet, daß man in wäßrige Zinn-II-halogenidlösungen 10 bis 100 Gew.-%, bezogen auf Zinn-II-halogenid, Alkylenoxid einleitet, die erhaltenen Fällungsprodukte von der Lösung abtrennt, auswäscht, bei Temperaturen von 100 bis 200° C trocknet, dann bei Temperaturen von 200 bis 700° C glüht und das Glühprodukt bis zum Erreichen der gewünschten Teilchengröße mahlt.Another process according to the invention is characterized in that 10 to 100% by weight, based on tin-II-halide, of alkylene oxide is introduced into aqueous tin-II-halide solutions, the precipitated products obtained are separated from the solution, washed out at temperatures of 100 dries to 200 ° C, then glows at temperatures from 200 to 700 ° C and grinds the glow product until the desired particle size is reached.

Als Alkylenoxid verwendet man insbesondere Ethylenoxid. Leitet man in eine Zinn-II-chloridlösung, die zur Dotierung ausreichende Mengen Zinn-II-fluorid gelöst enthält, Ethylenoxid ein, fällt Zinn-II-hydroxidchlorid, gegebenenfalls mit etwas Zinn-II-hydroxid, praktisch quantitativ aus.In particular, ethylene oxide is used as the alkylene oxide. If ethylene oxide is introduced into a tin (II) chloride solution which contains sufficient amounts of tin (II) fluoride in solution for doping, tin (II) hydroxide chloride, optionally with a little tin (II) hydroxide, precipitates practically quantitatively.

Hierbei wird gleichzeitig Ethylenchlorhydrin, das in der wäßrigen Phase verbleibt, gebildet. Wird dieses Fällprodukt gewaschen und zwischen 100 bis 250° C, vorzugsweise bei ca. 200° C getrocknet und anschließend in vorerwähnter Weise geglüht, so erhält man hierbei ein sehr gutes elektrisch leitfähiges Zinnoxid, das im Hinblick auf gewünschte Feinheit noch zusätzlich gemahlen werden kann.At the same time, ethylene chlorohydrin, which remains in the aqueous phase, is formed. If this precipitate is washed and dried between 100 to 250 ° C, preferably at about 200 ° C and then annealed in the aforementioned manner, a very good electrically conductive tin oxide is obtained, which can also be ground in view of the desired fineness.

Wird diese eben erwähnte Fällung durch Einleiten von Alkylenoxid zweckmäßigerweise Ethylenoxid ohne vorheriges Lösen von Zinn-II-fluorid vorgenommen, so wird ein fluoridfreies Zinn-II-chloridhydroxid ausgefällt, das gegebenenfalls noch etwas Zinn-II-hydroxid enthalten kann. Wird dieses Produkt nach mehrmaligem Waschen und anschließender Trocknung in vorerwähnter Weise geglüht, so wird hierbei ein fluoridfreies chloriddotiertes elektrisch leitfähiges Zinnoxid erhalten.If this precipitation just mentioned is expediently carried out by introducing alkylene oxide into ethylene oxide without first dissolving tin-II-fluoride, then a fluoride-free tin-II-chloride hydroxide is precipitated, which may also contain some tin-II-hydroxide. If this product is annealed in the aforementioned manner after repeated washing and subsequent drying, a fluoride-free, chloride-doped, electrically conductive tin oxide is obtained.

Chlorid- und/oder bromid- resp. jodiddotierte elektrisch leitfähige Zinnoxide werden in einfacher Weise auch dadurch hergestellt, daß man Mischungen von Zinn-II-oxid und Zinn-IV-oxid mit, bezogen auf Gemisch, bis zu 20 Gew.-% Zinn-II-halogeniden mahlend vermischt, das Gemisch in einem Temperaturbereich von 200 bis 700° C glüht und das Glühprodukt bis zum Erreichen der gewünschten Teilchengröße mahlt.Chloride and / or bromide or. iodine-doped electrically conductive tin oxides are also produced in a simple manner by mixing mixtures of tin-II-oxide and tin-IV-oxide with, based on the mixture, up to 20% by weight of tin-II-halide, the mixture glows in a temperature range of 200 to 700 ° C and grinds the glow product until the desired particle size is reached.

Die erfindungsgemäß hergestellten halogeniddotierten elektrisch leitfähigen Zinnoxide sind je nach Herstellung, Art und Menge der Dotierung grau bis hellfarben. Innerhalb der halogeniddotierten elektrisch leitfähigen Zinnoxide sind die mit Fluorid dotierten denen mit Chlorid, Bromid und Jodid dotierten in der elektrischen Leitfähigkeit und in ihrer Temperaturbeständigkeit etwas überlegen. Demgegenüber sind die Chlorid- und/oder Bromid- resp. Jodiddotierten den Fluoriddotierten im farblichen Aussehen insofern überlegen, als diese heller sind.The halide-doped electrically conductive tin oxides produced according to the invention are gray to light-colored depending on the production, type and amount of the doping. Within the halide-doped electrically conductive tin oxides, those doped with fluoride are somewhat superior to those doped with chloride, bromide and iodide in terms of their electrical conductivity and temperature resistance. In contrast, the chloride and / or bromide or. Iodine doping is superior to fluoride doping in terms of color in that they are lighter in color.

Die erfindungsgemäß hergestellten leitfähigen Zinn-IV-oxide weisen einen spezifischen Widerstand von < 50 Ω . m auf, wobei die gemessenen Werte bei fluordotiertem Zinn-IV-oxid meist < 10 Ω . m, insbesondere etwa 0,3 bis 2 Ω . m betragen.The conductive tin IV oxides produced according to the invention have a specific resistance of <50 Ω. m, the measured values for fluorine-doped tin IV oxide mostly <10 Ω. m, in particular about 0.3 to 2 Ω. m.

Die erfindungsgemäß hergestellten Verbindungen können aufgrund ihrer besonderen physikalischen Eigenschaften insbesondere als Füllstoff oder Pigment in Kunstoffen, Lacken, Farben, Papier, Textilien und Tonern verwendet werden.Due to their special physical properties, the compounds produced according to the invention can be used in particular as fillers or pigments in plastics, paints, paints, paper, textiles and toners.

Den erfindungsgemäßen Verfahren ist gemeinsam, daß die auf verschiedene Weise erhaltenen Produkte geglüht werden. Dieses Glühen erfolgt, wie bereits angegeben, bei etwa 200 bis 600° C. Bevorzugt ist ein Bereich von etwa 300 bis 500° C.The processes according to the invention have in common that the products obtained are annealed in different ways. As already stated, this annealing takes place at approximately 200 to 600 ° C. A range of approximately 300 to 500 ° C. is preferred.

Die erfindungsgemäß hergestellten halogeniddotierten elektrisch leitfähigen Zinnoxide sowie die unterschiedlichen Herstellungsverfahren werden durch nachfolgende Beispiele näher erläutert.The halide-doped electrically conductive tin oxides produced according to the invention and the different production processes are explained in more detail by the following examples.

Beispiel 1example 1

In einer Mörsermühle werden 250 g Zinn-II-oxid, 29,5 g Zinn-II-fluorid und 11,7 g Methanol durch 10minütiges Mahlen innig miteinander gemischt. Das so erhaltene Substanzgemisch wird anschließend in einer Korundschale 1 Stunde bei 500° C geglüht, wobei das Glühprodukt während der Glühzeit einmal krählend gemischt wird. Nach dem Erkalten wird das Glühprodukt nochmals in einer Mörsermühle 10 Minuten lang gemahlen.In a mortar mill, 250 g of stannous oxide, 29.5 g of stannous fluoride and 11.7 g of methanol are intimately mixed by grinding for 10 minutes. The mixture of substances obtained in this way is then annealed in a corundum dish at 500 ° C. for 1 hour, the annealing product being mixed by crying once during the annealing time. After cooling, the glow product is ground again in a mortar mill for 10 minutes.

Das so erhaltene elektrisch leitfähige Zinnoxid weist einen spezifischen Widerstand von 1,3 Ω . m auf. Der Zinn-II-gehalt beträgt < 0,3 %. Der Fluoridgehalt beträgt 0,9 %. The electrically conductive tin oxide thus obtained has a specific resistance of 1.3 Ω. m on. The tin II content is <0.3%. The fluoride content is 0.9%.

Beispiel 2Example 2

In einer Mörsermühle werden 250 g Zinn-II-oxid, 14,75 g Zinn-II-chlorid und 14,75 g Zinn-II-fluorid durch 10minütiges Mahlen innig miteinander vermischt. Die so erhaltene Stoffmischung wird in einer Korundschale 1 Stunde bei 300° C geglüht. Nach dem Erkalten wird das so erhaltene elektrisch leitfähige Zinnoxid nochmals 10 Minuten in einer Mörsermühle gemahlen.In a mortar mill, 250 g of stannous oxide, 14.75 g of stannous chloride and 14.75 g of stannous fluoride are intimately mixed by grinding for 10 minutes. The mixture of substances thus obtained is annealed in a corundum dish at 300 ° C. for 1 hour. After cooling, the electrically conductive tin oxide obtained in this way is ground again in a mortar mill for 10 minutes.

Das erhaltene elektrisch leitfähige Zinnoxid weist einen spezifischen Widerstand von 1 Ω . m auf. Der Zinn-II-gehalt beträgt 0,8 %. Der Fluoridgehalt liegt bei 0,49 %. Der Chloridgehalt liegt bei 0,3 %. The electrically conductive tin oxide obtained has a specific resistance of 1 Ω. m on. The tin II content is 0.8%. The fluoride content is included 0.49%. The chloride content is included 0.3%.

Beispiel 3Example 3

In einer Mörsermühle werden 125 g Zinn-IV-oxid und 14,75 g Zinn-II-fluorid durch 10minütiges Mahlen innig miteinander vermischt. Die so erhaltene Stoffmischung wird anschließend in einer Korundschale 1 Stunde bei 300° C geglüht. Das Glühprodukt wird nach dem Erkalten nochmals in einer Mörsermühle 10 Minuten lang gemahlen.In a mortar mill, 125 g of tin IV oxide and 14.75 g of tin II fluoride are intimately mixed by grinding for 10 minutes. The mixture of substances thus obtained is then placed in a corundum bowl Annealed for 1 hour at 300 ° C. After cooling, the annealed product is ground again in a mortar mill for 10 minutes.

Das so erhaltene elektrisch leitfähige Zinnoxid weist einen spezifischen Widerstand von 12 Ω . m auf. Der Zinn-II-gehalt beträgt < 0,3 %. Der Fluoridgehalt beträgt 0,9 %. The electrically conductive tin oxide thus obtained has a specific resistance of 12 Ω. m on. The tin II content is <0.3%. The fluoride content is 0.9%.

Beispiel 4Example 4

250 g Zinn-II-oxid werden in einem Becherglas mit einer 70 %igen methanolischen Zinn-II-chloridlösung 20 Minuten lang gerührt. Im Anschluß daran wird die überstehende wäßrige Phase abdekantiert. Das so erhaltene Produkt wird 1 Stunde bei 200° C getrocknet und anschließend in einer Korundschale 1 Stunde bei 500° C geglüht. Während der Glühzeit wird das Produkt einmal krählend gemischt. Nach dem Erkalten wird das Glühprodukt in einer Mörsermühle gemahlen.250 g of stannous oxide are stirred in a beaker with a 70% methanolic stannous chloride solution for 20 minutes. The supernatant aqueous phase is then decanted off. The product thus obtained is dried at 200 ° C. for 1 hour and then annealed in a corundum dish at 500 ° C. for 1 hour. During the glow period, the product is mixed by crying once. After cooling, the glow product is ground in a mortar mill.

Das so erhaltene elektrisch leitfähige Zinnoxid weist einen spezifischen Widerstand von 8 Ω . m auf. Der Zinn-II-gehalt beträgt 0,5 %. Der Chloridgehalt beträgt < 0,3 %. The electrically conductive tin oxide thus obtained has a specific resistance of 8 Ω. m on. The tin II content is 0.5%. The chloride content is <0.3%.

Beispiel 5Example 5

In einer Mörsermühle werden 250 g Zinn-II-oxid und 29,5 g Zinn-II-jodid durch 10minütiges Mahlen innig miteinander gemischt. Das so erhaltene Stoffgemisch wird in einer Korundschale 1 Stunde bei 500° C geglüht. Während der Glühzeit wird das Produkt einmal krählend gemischt. Anschließend wird das Glühprodukt nach dem Erkalten nochmals 10 Minuten lang in einer Mörsermühle gemahlen.In a mortar mill, 250 g of stannous oxide and 29.5 g of stannous iodide are intimately mixed by grinding for 10 minutes. The mixture of substances thus obtained is annealed in a corundum dish at 500 ° C. for 1 hour. During the glow period, the product is mixed by crying once. After cooling, the glow product is then ground again in a mortar mill for 10 minutes.

Es wird ein elektrisch leitfähiges Zinnoxid erhalten, das einen spezifischen Widerstand von 36 Ω . m aufweist. Der Zinn-II-gehalt beträgt 1,8 %. Der Jodidgehalt beträgt 1,2 %. An electrically conductive tin oxide is obtained which has a specific resistance of 36 Ω. m has. The tin II content is 1.8%. The iodide content is 1.2%.

Beispiel 6Example 6

In einer Mörsermühle werden 250 g Zinn-II-oxid und 34,0 g Bromwasserstoffsäure (48 %ig) durch 10minütiges Mahlen innig miteinander vermischt. Das so erhaltene Stoffgemisch wird in einer Korundschale 1 Stunde bei 500° C geglüht. Während der Glühzeit wird das Produkt einmal krählend gemischt. Das Glühprodukt wird nach dem Erkalten nochmals 10 Minuten lang in einer Mörsermühle gemahlen.In a mortar mill, 250 g of stannous oxide and 34.0 g of hydrobromic acid (48% strength) are intimately mixed with one another by grinding for 10 minutes. The mixture of substances thus obtained is annealed in a corundum dish at 500 ° C. for 1 hour. During the glow period, the product is mixed by crying once. After cooling, the annealed product is ground again in a mortar mill for 10 minutes.

Das so erhaltene elektrisch leitfähige Zinnoxid weist einen spezifischen Widerstand von 40 Ω . m auf. Der Zinn-II-gehalt beträgt < 0,3 %. Der Bromidgehalt beträgt 1,0 %. The electrically conductive tin oxide thus obtained has a specific resistance of 40 Ω. m on. The tin II content is <0.3%. The bromide content is 1.0%.

Beispiel 7Example 7

In einem 2-l-Vierhalskolben mit Rückflußkühler, Thermometer, Rührer und Schliffstopfen werden 670 g wäßrige Zinn-II-chloridlösung (38,3 %ig) vorgelegt. Dazu werden unter Rühren 28,4 g festes Zinn-II-fluorid gegeben. Diese Stoffmischung wird so lange gerührt (ca. 20 Minuten), bis eine nahezu klare Lösung erhalten wird. In diese Lösung werden 101,2 g Ethylenoxid langsam eingeleitet (innerhalb von 5 Stunden). Aufgrund der exothermen Reaktion erwärmt sich die Reaktionsmischung auf ca. 45° C.670 g of aqueous tin-II-chloride solution (38.3% strength) are placed in a 2-liter four-necked flask with a reflux condenser, thermometer, stirrer and ground glass stopper. 28.4 g of solid tin-II-fluoride are added with stirring. This mixture of substances is stirred (approx. 20 minutes) until an almost clear solution is obtained. 101.2 g of ethylene oxide are slowly introduced into this solution (within 5 hours). Due to the exothermic reaction, the reaction mixture warms up to approx. 45 ° C.

Nach wenigen Minuten Einleitungszeit wird basisches Zinn-II-chlorid mit kleinen Mengen Zinn-II-hydroxid unter gleichzeitiger Bildung von Ethylenchlorhydrin ausgefällt. Nach Einleiten der gesamten Ethylenoxidmenge wird das so erhaltene Fällprodukt abgenutscht. Nach zweimaligem Waschen mit jeweils ca. 250 ml Wasser wird das Produkt im Rotationsverdampfer im Vakuum (3 mm Hg) 2 Stunden lang getrocknet.After a few minutes of introduction, basic tin-II-chloride is precipitated with small amounts of tin-II-hydroxide with simultaneous formation of ethylene chlorohydrin. After the entire amount of ethylene oxide has been introduced, the precipitate obtained in this way is filtered off with suction. After washing twice with about 250 ml of water each time, the product is dried in a rotary evaporator in vacuo (3 mm Hg) for 2 hours.

Das so erhaltene Produkt wird anschließend in einer Korundschale 1 Stunde bei 500° C geglüht. Während der Glühzeit wird das Produkt einmal krählend gemischt. Das Glühprodukt wird nach dem Erkalten 10 Minuten lang in einer Mörsermühle gemahlen.The product obtained in this way is then annealed in a corundum dish at 500 ° C. for 1 hour. During the glow period, the product is mixed by crying once. After cooling, the annealed product is ground in a mortar mill for 10 minutes.

Es wird ein elektrisch leitfähiges Zinnoxid mit einem spezifischen Widerstand von 2 Ω . m erhalten. Der Zinn-II-gehalt beträgt < 0,3 %. Der Chloridgehalt beträgt 0,5 %. Der Fluoridgehalt beträgt 1,2 %. It becomes an electrically conductive tin oxide with a specific resistance of 2 Ω. m received. The tin II content is <0.3%. The chloride content is 0.5%. The fluoride content is 1.2%.

Beispiel 8Example 8

Es wird in analoger Weise wie bei Versuch 7 gearbeitet, jedoch ohne Einsatz von Zinn-II-fluorid.The procedure is analogous to experiment 7, but without the use of stannous fluoride.

Hierbei wird ein elektrisch leitfähiges Zinnoxid mit einem spezifischen Widerstand von 12 Ω . m erhalten. Der Zinn-II-gehalt beträgt < 0,3 %. Der Chloridgehalt beträgt 0,4 %. This is an electrically conductive tin oxide with a specific resistance of 12 Ω. m received. The tin II content is <0.3%. The chloride content is 0.4%.

Beispiel 9Example 9

In einem 3-l-Becherglas werden 950 ml Zinnsulfatlösung mit 125 g Sn(II)/l und 400 ml einer 20 %igen Zinn-II-fluoridlösung unter Rühren vermischt.950 ml of tin sulfate solution with 125 g of Sn (II) / l and 400 ml of a 20% tin-II-fluoride solution are mixed with stirring in a 3-liter beaker.

Zu dieser Mischung werden unter Rühren 950 ml einer 16,5 %igen Ammoniumhydrogencarbonatlösung bei Raumtemperatur zugegeben.950 ml of a 16.5% ammonium hydrogen carbonate solution are added to this mixture at room temperature with stirring.

Es wird ein weißes Fällprodukt erhalten das fünfmal mit jeweils 2,5 l Wasser dekantierend gewaschen wird. Das so gewaschene Fällprodukt wird anschließend in einer Porzellanschale bei 110° C (12 Stunden) getrocknet und dann in einem Korundtiegel bei 500° C 1 Stunde geglüht. Während der Glühzeit wird das Produkt einmal krählend gemischt. Nach dem Glühen und Erkalten wird das Produkt über ein 630-µm-Sieb abgesiebt und der Siebdurchgang nochmals 15 Minuten bei 500° C geglüht. Dieses so erhaltene Glühprodukt wird über ein 100-µm-Sieb abgesiebt.A white precipitate is obtained which is washed five times with 2.5 l of water each time. The precipitated product washed in this way is then dried in a porcelain dish at 110 ° C. (12 hours) and then annealed in a corundum crucible at 500 ° C. for 1 hour. While the glowing time, the product is mixed once crowing. After annealing and cooling, the product is sieved through a 630 μm sieve and the sieve pass is annealed again at 500 ° C. for 15 minutes. The glow product thus obtained is sieved through a 100 μm sieve.

Das so als Siebdurchgang erhaltene elektrisch leitfähige Zinnoxid hat einen spezifischen Widerstand von 0,3 Ω . m. Der Zinn-II-gehalt beträgt < 0,3 %. Der Fluoridgehalt beträgt 1 %. The electrically conductive tin oxide thus obtained as a sieve has a specific resistance of 0.3 Ω. m. The tin II content is <0.3%. The fluoride content is 1 %.

Claims (9)

  1. Process for the preparation of an electroconductive tin (IV) oxide containing a maximum of 2% of divalent tin and from 0.1 to 2.5% of halides, characterized in that tin(II) oxide or tin(IV) oxide is mixed with, based on the mixture, up to 20% by weight of tin(II) fluoride or an equivalent amount of hydrofluoric acid with grinding, the mixture is ignited in a temperature range of from 200 to 700°C, and the ignition product is ground until the desired particle size has been reached.
  2. Process according to Claim 1, characterized in that low-molecular-weight alcohols are added to the mixture of tin(II) oxide and tin(II) fluoride or hydrofluoric acid.
  3. Process according to Claim 2, characterized in that methanol or ethanol is added to the mixture.
  4. Process for the preparation of an electroconductive tin(IV) oxide containing a maximum of 2% of divalent tin and from 0.1 to 2.5% of halides, characterized in that first basic tin(II) compounds and/or basic tin(II) hydroxides are precipitated from tin(II) salt solutions in a manner known per se, the resultant precipitation products are washed a number of times and then stirred with from 5 to 70% by weight, based on the precipitated basic tin(II) compounds, of tin(II) fluoride in the form of an aqueous solution for a period of from 5 to 60 minutes, the doped precipitation products are separated from the solution, washed, dried at temperatures of from 100 to 200°C and then ignited at temperatures of from 200 to 700°C, and the ignition product is ground until the desired particle size has been reached.
  5. Process for the preparation of an electroconductive tin(IV) oxide containing a maximum of 2% of divalent tin and from 0.1 to 2.5% of halides, characterized in that basic tin(II) compounds and/or basic tin(II) hydroxides are precipitated from tin(II) salt solutions in a manner known per se, the precipitation is carried out in the presence of from 1 to 70% by weight, based on the precipitated basic tin(II) compounds, of tin(II) fluoride, the doped precipitation products are separated from the solution, washed, dried at temperatures of from 100 to 200°C and then ignited at temperatures of from 200 to 700°C, and the ignition product is ground until the desired particle size has been reached.
  6. Process for the preparation of an electroconductive tin(IV) oxide containing a maximum of 2% of divalent tin and from 0.1 to 2.5% of halides, characterized in that from 10 to 100% by weight, based on tin(II) halide, of alkylene oxide is passed into agueous tin(II) halide solutions, the resultant precipitation products are separated from the solution, washed, dried at temperatures of from 100 to 200°C and then ignited at temperatures of from 200 to 700°C, and the ignition product is ground until the desired particle size has been reached.
  7. Process according to Claim 6, characterized in that the alkylene oxide used is ethylene oxide.
  8. Process for the preparation of an electroconductive tin(IV) oxide containing a maximum of 2% of divalent tin and from 0.1 to 2.5% of halides, characterized in that mixtures of tin(II) oxide and tin(IV) oxide are mixed with, based on the mixture, up to 20% by weight of tin(II) halides with grinding, the mixture is ignited in a temperature range of from 200 to 700°C, and the ignition product is ground until the desired particle size has been reached.
  9. Process according to Claim 1, 4, 5, 6 or 8, characterized in that the mixture obtained in each case is ignited in a temperature range of from 300 to 600°C.
EP91102065A 1990-02-26 1991-02-14 Electrically conductive stannic oxide Expired - Lifetime EP0448946B1 (en)

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JP3346584B2 (en) * 1991-03-29 2002-11-18 三井金属鉱業株式会社 Fibrous conductive filler and method for producing the same
DE4213747A1 (en) * 1992-04-25 1993-10-28 Merck Patent Gmbh Electroconductive pigment with outer coating of tin or titanium di:oxide - is doped with halogen on opt. coated metal, metal oxide, silica or silicate substrate and used in plastics or lacquer
DE59304334D1 (en) * 1992-04-25 1996-12-05 Merck Patent Gmbh Electrically conductive pigment
KR940000377A (en) * 1992-06-11 1994-01-03 아끼자와 다끼시 Conductive tin oxide fine powder and its manufacturing method
EP0586003A3 (en) * 1992-09-04 1994-06-15 Metallgesellschaft Ag Electrically-conductive filler and process for manufacturing the same
DE4318568A1 (en) * 1993-06-04 1994-12-08 Goldschmidt Ag Th Process for the preparation of feinstteiligem, electrically conductive tin-IV-oxide
GB9321481D0 (en) * 1993-10-18 1993-12-08 Alcan Int Ltd Tin oxide
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DE10051872C2 (en) * 2000-10-19 2002-11-21 Merck Patent Gmbh Electrically conductive pigments and processes for their production
DE102014008186A1 (en) 2014-06-10 2015-12-31 Merck Patent Gmbh Laser-markable and laser-weldable polymeric materials
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US3537890A (en) * 1967-03-03 1970-11-03 Rca Corp Conductive coatings of tin oxides
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US4265974A (en) * 1976-11-01 1981-05-05 Gordon Roy G Electrically conductive, infrared reflective, transparent coatings of stannic oxide
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US4246143A (en) * 1978-07-12 1981-01-20 Matsushita Electric Industrial Co., Ltd. Process of preparing conductive tin dioxide powder
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